Vat dyestuffs containing allyl groups



United States Patent 3,242,176 VAT DYESTUFFS CONTAINHN G ALLYL GROUPS Walter Jenny and lstvan Hari, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, 21 Swiss comany l lo Drawing. Filed May 31, 1962, Ser. No. 198,705 Claims priority, application Switzerland, June 2, 1961, 6,486/ 61 Claims. (Cl. 260249) The present invention provides vat dyestuffs that contain at least one allyl-mercapto or allyl-sulfone group, which group may be bound to an aliphatic chain or preferably to an aromatic nucleus of the vattable system.

The allyl-SO -group, that is to say, the

may be bound directly to the vattable residue or through a nitrogen bridge, for example, through a bridge of the formula l IC n-I Zn-l in which n is a low positive whole number, advantageously 1.

The term vat dyestuffs includes dyestuifs which are capable of conversion by reduction into a so-called leuco form or vat which has better aflinity for natural and regenerated cellulose fibers than has the n0n-redl10ed form, and which can be reconverted by oxidation into the original chromophoric system. As suitable vat dyestutfs there may be mentioned more especially those of the anthraquinone series, for example, those which contain an unmodified 9rl0-dioxoanthracene ring, and also those anthraquinones that also contain fused carbocyclic or heterocyclic rings or which consist of a plurality ranthraquinone units, and also vat dyestuifs of the naphthalene 0r perylene tetracarboxylic acid series or of the pyrenequinone or indigoid series. In addition to at least one allyl grouping of the kind defined above the dyestuffs may also contain substituents usual in vat dyestuffs, for example, halogen atoms, alkoxy groups, acylamino groups or alkyl groups.

The invention also provides a process for the manufacture of the above new dyestuffs wherein (a) a vat dyestuff that contains a mobile halogen atom, for example, a vat dyestutf that contains a sulfonic acid halide group or a chlorotriazinyl-amino group, is condensed with an amine that contains an allylmerc-apto group or an allyl- SO -group, or (b) a vat dyestutf that contains at least one exchangeable halogen atom bound to a carbon atom or another exchangeable group, for example, an a-sulfo group, is reacted with allyl-mercaptan, or (c) a vat dyestutf containing an acylatable amino group or a corresponding intermediate product is reacted with an acylating agent, which contains an allyl-mercapto group or an allyl- SO -group if the starting dyestuif does not contain such an allyl group, or (d) a vat dyestuiT that contains a mercapto group is etherified with an allyl halide.

As starting materials for method (a) of the process there are used vat dyestuffs that contain, for example, at least one sulfonic acid chloride group or chlorotriazinyl group or chloropyrimidyl-amino group, or.a chloroalkylsulfone or a sulfonic acid chloroalkyl-amide group or a sulfonic acid fl-sulfatoalkylamide group. Of special interest are vat dyestuffs that contain two sulfochloride groups. As examples of suitable starting materials there may be specially mentioned those of the anthraquinone series: 1:5 dibenzoylamino-anthraquinone disulfochloride, dibenzanthrone disulfochloride, iso-dibenzanthrone disulfochloride, and the sulfochlorides of anthanthrone, dibenzpyrenequinone, pyranthrone, acedianthrone, flavanthrone, indanthrone, N:N-diethyl-dipyrazole-anthronyl, N:N-diisopropyl-dipyrazole-anthronyl, anthraquinone- 2:1 (N) 1':2'-(N)-naphthacridone, 1:1" dianthrimidecarbazole and 2':2"-diphenyl-anthraquinone-1:2(N)-5 :6 (N -dithiazole.

Besides the sulphochlorides of the anthr-aquinone series already mentioned, there may be used sulphochlorides of indigoid vat dyestuffs or of perylene tetracarboxylic acid diimides or of perinone dyestuiis. The aforesaid sulfochlorides may be obtained by treating the appropriate vat dyestuifs with chlorosulfonic acid, if necessary, with parti-al hydrolysis of the polysulfochlorides so obtained, or by reacting the appropriate sulfonic acid with acid-halogenating agents, such as phosphorus halides, thionyl chloride or chlorosulfonic acid by known methods. Another method of obtaining the sulfochlorides to be used as starting material consists in acylating an amino-anthraquinone with benzoic acid sulfonic acid dichloride to form a chlorosulfonyl-benzoylamino-anthraquinone. In method (a) of the process there may also be used as starting materials reaction products of aminoanthraquinones with halogen-pyrimidines or halogen-triazines, such as cyan-uric chloride, that contain at least one exchangeable chlorine atom, for example, a compound of the formula ample, with an amine of the formula or with an amine of the formula The reaction of the vat dyestutf containing mobile halogen atoms, for example, the reaction of one of the aforesaid sulfochlorides with the amine containing an allylmercapto or allyl-sulfone group may be carried out in an inert organic solvent, for example, nitrobenzene, chlorobenzene or ortho-dichlorobenzene, at a raised temperature. However, since the sulfochlorides are generally obtained in aqueous suspension during their preparation, it is of advantage to carry out the reaction with the amine in aqueous medium, advantageously in the presence of an agent capable of binding acid, for example, sodium acetate, sodium hydroxide or sodium carbonate. The molar ratio of the components is advantageously so chosen that at least one mol of amine is used for each chlorine atom of the vat dyestuff that is capable of reaction.

The starting materials for method (b) of the present process are advantageously anthraquinone vat dyestufifs that contain one or two exchangeable halogen atoms bound to a carbon atom of the dyestufis molecule, for example, the monoor di-(chloroethylsulfones) of 1:5- dibenzoyl-amino-anthraquinone or of dibenZanthro-ne or of iso-dibenzanthrone, and the chlorethyl-sulfones of sulfonic acid-N:fi-chlorethylamides of anthanthrone, dibenzpyrenequinone, pyranthrone, acedianthrone, flavanthrone, indanthrone, N:N-diethyl-dipyrazole-anthronyl, N :N'-diisopropyl-dipyrazole, anthronyl, anthraquinone-2:1(N): 1':2'(N) -naphthacridone, 1: 1'-dianthrimide-carbazole or 2':2-diphenylanthraquinone-1:2(N); 5 6 (N)-dithiazole. Besides the aforesaid chlorethyl-sulfonamides and chlorethyl-sulfones of the anthraquinone series, there may be used vat dyestuffs containing halogen atoms or sulfo groups bound aromatically, such as the oc-ChlOIO-, a-bI'O- moor a-sulfo-anthraquinones containing benzoylamino groups, and also chlorotriazinyl-amino-anthraquinones which likewise yield the vat dyestuffs of the invention when reacted with allyl-mercaptan or a metal salt thereof.

As starting materials for method (c) of the process there are used amino-anthraquinones or vat dyestuffs that contain acylatable amino groups, for example, 1:5-di amino-anthraquinone, 1-amino-S-benzylamino-anthraquinone, 4 amino-anthraquinone-2:1(N)-acridones, 4:4'-, 4:5'- or 5:5-diamino-1:1-dianthrimide carbazole, aminopyranthrone, monoand diamino-acedianthrone, aminoisodibenzanthrone, amino-dibenzanthrone, amino-anthraquinone, amino-flavanthrone, amino-pyranthrone, 4- or 5- amino-l:1'-dianthrimidecarbazole, 4- or 5-amino-5-benzoyl amino-dianthrimide carbazole, 4-amino-4-benzoylamino-dianthrimide-carbazole or amino-dibenzpyrenequinone, and also monoand diamino-trianthrimide-carbazoles, for example, 8:8"-diamino-1':1:5:1-trianthrimide-carbazole, and perylene-tetracarboxylic acid-di-(paraor meta-aminophenyl)-imide, and the compounds of the formulae (H) ITlI'Iz N\ fl) l i I IHE O (X==O or S) and and of the formula X X X 0 X l l l H I X o NHR-NI'I o X in which at least four of the symbols X represent hydrogen atoms and the others represent -NH groups, and R represents a triazine residue or a CORCO group, in which R represents an arylene residue.

As acylating agents that contain an allyl residue bound through an S or SO bridge, there may be mentioned more especially acid halides, advantageously those of the formulae in which R represents a benzene residue or an alkylene residue. The said acylating agents are advantageously 4- obtained by reacting the appropriate mercapto-benzoic acids with allyl halides, if required, with subsequent oxidation to allyl-sulfone benzoic acids. There may also be used as acylating agents, for example, compounds of the formula The reaction of the aminoanthraquinones or vat dyestuffs containing amino groups with the acylating agent is carried out advantageously in an inert organic solvent, for example, nitrobenzene, chlorobenzene or orthodichlorobenzene, at a raised temperature. The molar ratio of the components is advantageously so chosen that there is approximately one carboxylic acid chloride group or group of the formula of the acylating agent for each amino group of the anthraquinone radical.

In method (d) of the process a vat dyestuif that contains an HS group bound, for example, to an aliphatic chain or to an aromatic nucleus, is etherified with an allyl halide, especially allyl chloride or allyl bromide. This etherification is carried out in aqueous solution or in an organic solvent, such as alcohol, benzene, toluene or the like, advantageously in the presence of an agent capable of binding the hydrogen halide split off, for example, in the presence of an alkali metal hydroxide.

The vat dyestuffs of the invention, which contain a carbazole ring or an oxidazole ring, can also be made by a method in which appropriate starting materials, for example, allyl-sulfonylor allyl-mercapto-anthrimides, are carbazolised to allyl-sulfonylor allyl-mercapto-anthrimide-carbazoles with aluminum chloride by methods in themselves known, or in which the oxidazole ring is introduced into allyl-SO or into allyl-mercapto-dianthraquinone-carboxylic acid hydrazides by splitting off of water, for example, by means of concentrated sulfuric acid or oleum, if desired, with simultaneous sulfonation.

Vat dyestuffs that contain allyl-mercapto groups or allyl-sulfone groups can also be obtained by subjecting ortho-carboxyarylamino-allyl-mercapto-anthraquinones or allyl-SO 1-arylamino-anthraquinone-2-carboxylic acids to ring closure to form acridones, or by the alkaline treatment of 1-amino-2 bromo-allylmercapto-anthraquinones or Z-amino-1-chloroallyl-sulfonyl-anthraquinones, for example, at to C., in an organic solvent in the presence of an alkali carbonate to form the corresponding indanthrones.

The vat dyestuffs of the invention can be worked up The filtered dyestuffs may be dried, if desired, after the addition of buffers or neutral or weakly alkaline extenders. The drying is advantageously carried out at not too high a temperature and, if required, under reduced pressure.

The new dyestufls are suitable for dyeing or printing a very wide variety of materials, but especially for dyeing or printing tex-t-ile materials of natural or regenerated cellulose by the usual vat dyeing or printing methods. The dyeings and prints produced therewith are generally distinguished by their very good properties of wet fastness, and especially by their good 'fastness to soda boiling. In the case of some of the dyestufls of the invention, it is possible that they combine chemically with the fiber.

Some of the dyeings obtained with the dyestuffs of the invention are fast to dry-cleaning.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated, and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

Example I 2 parts of 1:S-diamino-anthraquinone are dissolved hot in 40 of ortho'dichlorobenzene. To the solution so obtained are added 3.56 parts of 4-allyl mercapto-benzoyl chloride, and the reaction mixture is maintained at the boil for 30 minutes under reflux. The dyestuff, which precipitates on cooling, has the probable formula and is isolatedby filtration, washed with hot alcohol and dried. It can be recrystallized from chlorobenzene and then melts at 268 to 270 C.

When applied, "for example, by the dyeing prescription given below, the dyestuff dyes cotton and regenerated cellulose yellow tints possessing excellent properties of wet fastness.

A similar dyestuff, but one yielding markedly greener tints, is obtained by acylating l-amino-S-benzoylaminoanthraquinone with 4-allylmercapto-benzoyl chloride.

4-allylmercapto-benzoic acid can be prepared in the following manner: parts of 4-mercapto-benzoic acid are dissolved in 150 parts of ethyl alcohol of 75% strength, which contains 9 parts of potassium hydroxide. To the solution so obtained are added 7.5 parts of allyl chloride, and the whole is maintained at the boil for one hour under reflux. The solution is diluted with 150 parts of water and cooled to- 10 C., and is rendered acid to Congo with dilute sulfuric acid. The precipitated product is isolated by filtration, washed with a little cold water, and recrystallized from ethyl alcohol. The 4-allylmercapto-benzoic acid is obtained in excellent yield in the form of white needles melting at 114 C. The corresponding acid chloride can be obtained in the usual manner by the action of thionyl chloride. It is a pale yellow oil that boils at 170 C. under a pressure of 14 mm. of Hg.

Dyeing prescripti0nl.14 parts of the dyestulf obtained as described in the first paragraph of this example are finely ground in a ball mill for 24 hours with 126 parts of a neutral solution of 125 parts of dinaphthylmethane disulfonic acid in 1000 parts of water.

75 parts of the paste so obtained are suspended in 250 parts of warm Water. The dyestuff suspension so -obtained is introduced into a solution, having a temperature Example 2 2 parts of l-aminoanthraquinone are dissolved hot in 60 parts of ortho-dichlorobenzene. To the solution so obtained are added 3.4 parts of 2-(4'-allylsulfonylphenyl)-benzthiazole-6-carboxylic acid chloride, and the reaction mixture is maintained at the boil for minutes under reflux. The dyestutf, which precipitates on cooling has the probable formula The dyestutf so obtained is isolated by filtration, washed, and recrystallized from nitrobenzene.

The dyestuff so obtained dyes cotton and regenerated cellulose pure green-yellow tints possessing excellent properties of wet fastness when applied, for example, by the dyeing prescription given in the last paragraph of Example 1.

A dyestuif that is equally fast, but yields considerably redder tints, is obtained by acylating 1-arnino-5-benzoylamino-anthraquinone with 2-(4-allylsulfonyl-phenyl)- benzthiazole-6-carboxylic acid chloride.

2 (4' allylsulfonyl-phenyl)-benzthiazole-6-carboxylic acid can be prepared in the following manner: 7.5 parts of 5-carboxy-2-amino-thiophenol hydrochloride are dissolved at 80 C. in parts of pyridine. To the solution so obtained are added 8.9 parts of 4-allyl-sulfonyl-benzoyl chloride, and the Whole is stirred for 1 hour at 80 C. When the reaction mixture has cooled, the precipitated crystals are isolated by suction filtration, washed with hydrochloric acid of 5% strength and Water, and then dried at to C. The new acid crystallizes from a mixture of glacial acetic acid and dimethylformamide (1:1) in the form of white crystals, which melt at 284 to 285C. The corresponding acid chloride can be obtained in the usual manner by reaction with thionyl chloride under reflux. It crystallizes from a mixture of benzene and nitrobenzene (5:1) in the form of white crystals which melt at 225 to 226 C.

Example 3 2 parts of 1:4-dia1nino-2-acetyl-anthraq uinone are dissolved hot in parts of ortho-dichlorobenzene. To the solution so obtained are added 2.72 parts of 2-(4'-allylsulfonyl-phenyl)benzthiazole-6-carboxylic acid chloride, the whole is brought to the boil and maintained at the boil for 30 minutes under reflux. The dyestuflf which precipitates in the form of dark blue crystals on cooling, has the probable formula The dyestutf is isolated by suction filtration, washed with hot alcohol and dried.

The dyestuff so obtained dyes cotton and regenerated cellulose pure blue tints possessing excellent properties of fastness, when applied, for example, according to the dyeing, prescription given in the last paragraph of Example 1.

Example 4 To a solution of 2.72 parts of 4-allylsulfonyl-benzoyl chloride in 80 parts of dry nitrobenzene is added, at 30 C., a suspension of 3 parts of 4:4-diamino-1:1- dianthrirnide-carbazole in 30 parts of nitrobenzene, and the whole is stirred for 6 hours at 140 to 145 C. and for 2 hours at 170 to 175 C. When the reaction mixture is cold, the dyestufr of the formula which precipitates in the form of crystals, is isolated by filtration, washed with nitrobenzene and hot alcohol, and dried in vacuo at 70 C.

When dry, the dyestuif is in the form of lustrous black crystals (plates), and dyes cotton and regenerated ce1- lulose grey tints possessing very good general properties of fastness when applied, for example, according to the dyeing prescription given in Example 1.

4-allyl-sulfone-benzoic acid can be prepared in the following manner: A fine suspension of 4 parts of benzoic acid-4-allyl sulfide (see Example 1) is heated to 85 C. in 38 parts of water. To this suspension are added 15 parts of hydrogen peroxide of 30% strength, and the whole is stirred for hours at 85 C. After cooling to C., the solution so formed is stirred for a further 30 minutes, the precipitate is isolated by suction filtration, dried and recrystallized from nitrobenzene. The 4-allyl-sulfonebenzoic acid so obtained is in the form of white crystals that melt at 172 to 176 C.

The acid chloride can be prepared in the usual manner by reaction with thionyl chloride under reflux. It is in the form of white crystals that melt at 114 to 115 C.

Example 5 To a fine suspension of 11.0 par-ts of monoamino-acedianthrone in 140 parts of nitrobenzene are added, at

C., 6.0 parts of 4-allylmercapto-benzoyl chloride and 0.5 part by volume of pyridine. The whole is stirred for 3 hours at 160 to 170 C., and then allowed to cool. The dyestuif of the formula which is isolated, by filtration, is washed with hot ethanol and dried. The dyestulf so obtained is a red-brown powder that dyes cotton and regenerated cellulose attractive and very fast brown tints, when applied according to the method described in Example 1.

Example 6 To a fine suspension of 4.95 parts of 5:5-diamino-l:1'- dianthrimide-carbazole in 120 parts of nitrobenzene are added, at 120 C., 4.7 parts of 3-allyl-mercapto-benzoyl chloride. The whole is stirred for 1 hour at 165 C. and allowed to cool. The dyestuff of the formula O-o O-NH Example 7 4.9 parts of 4: 6-dichloro-2-[(5)-benzoylamino-anthraquinonyl (1) amino] 113:5 triazine are stirred into' 26 parts of nitrobenzene and 5 parts by volume of NzN- diethyl-aniline at room temperature. 0.75 part of allyl mercaptan is then added, and the whole is stirred for 2 hours at 50 C., 2 hours at 100 C. and 2 hours at to C.. and then filtered hot. The filtrate is allowed to cool, and is then diluted with a mixture of parts of a mixture of ethanol and ether (2:1). The dyestufr' which then precipitates has the formula It is isolated by suction filtration, washed Well with ether and dried. The dyestuff so obtained dyes cotton and regenerated cellulose pure strong yellow tints when applied according to the dyeing prescription given in Example 1.

Example 8 h) NHz N\ is isolated by filtration, heated to the boil in hot ethanol, isolated by suction filtration, and then dried. The dyestuif so obtained dyes cotton and regenerated cellulose strong blue tints possessing excellent properties of fastness, when applied by the dyeing prescription given in Example 1. i

Example 9 a 18 parts of a moist paste of the disodium salt of 4: dimercapto-anthanthrone of strength are dissolved in 1500 parts of water at C. The solution so obtained is filtered hot, and then 8 parts of allyl chloride in 50 parts of ethanol are added, the whole is stirred for 1 hour at 80 C., and then allowed to cool. The dyestuff which precipitates has the formula and is isolated by suction filtration, suspended in ethanol, the suspension is brought quickly to the boil, and the dyestufl is isolated by filtration and then dried.

The product so obtained is a reddish blue powder that dyes cotton and regenerated cellulose pure violet tints when applied according to the dyeing prescription given in Example 1.

The starting material can be prepared as follows:

To a fine suspension of 10 parts of 4:10-dibroman- .thanthrone in 4000 parts of ethanol is added a filtered solution of 200 parts of sodium hydrosulfide of 72% strength in 800 parts of water. The whole is stirred .for 24 hours at to C. in a porcelain autoclave, .and then allowed to cool. The green crystalline precipitate is isolated by filtering with suction, and washed .with a little ethanol. The product is obtained in excel- .lent yield in the form of a dark violet mass.

. Example 10 2.45 parts of 4:6-dichloro-2-[S-benzoylaminoanthraquinonyl-(l)-amino]-1]3]5-triazine are stirred into 15 parts of nitrobenzene and 5 parts by volume of NzN- diethyl-aniline at C. 1.0 part of -4-allyl-sulfonylaniline [B.R. Baker, J. Org. Chem, 15, 415 (1950)] is strewn in, the whole is stirred for 6 hours at to C., cooled, and then slowly diluted with parts of a mixture of benzene and ether (1:1). The dyestuif which then precipitates has the formula -It is isolated by suction filtration, washed well with ether, and then dried. It is a khaki-coloured product containing chlorine and sulfur that dyes cotton and re- .generated cellulose strong yellow tints possessing good .properties of fastness, when applied according to the dyeing prescription given in Example 1.

1 Example 11 To a suspension of 1.12 parts of 2-chloro-4:6-di-(a anthraquinonylamino)-123:5-triazine in 25 parts of nitrobenzene is added 1.0 part of 4.aminophenyla allyl sul- :fone [B. R. Baker, I. Or. Chem, 15, 415 (1950)] and the whole is stirred for 16 hours at C. The solu- ;tion so obtained is allowed to cool. The dyestuff of the hot ethanol and dried. The dark, khaki-coloured product so obtained contains no chlorine, and dyes cotton and regenerated dellylose strong pure yellow tints possessing very good properties of fastness, when applied according to the dyeing prescription given in Example 1.

Example 12 A fine suspension of 1.3 parts of 2:5-bis-(1':4-diamino-2-anthraquinonyl)-1:324-oxdiazole and 1.25 parts of 3-allyl-sulfonyl benzoyl chloride in 35 parts of nitrobenzene and 0.5 part by volume of pyridine is heated to 170 to 175 C. in a period of 1 hour. The suspension is stirred for 3 hours at that temperature and allowed to cool. The isolated dyestuff of the formula V (I? NHB HzN O O NH O I o o H2C=HCHzO-O2S -SOzOI-Ig-O H=CII2 is boiled for a short time in ethanol, isolated while hot by suction filtration, and then dried. The dark blue sulfur-containing product dyes cotton and regenerated cellulose strong dark violettish blue tints possessing excellent porperties of fastness when applied, for example, according to the dyeing prescription given in the last paragraph of Example 1.

Example 13 A fine suspension of 2.0 parts of disulfochloride of the formula 1.7 parts of 4-aminopheny1-allylsulfone and 0.2 part of 50 anhydrous sodium carbonate in 30 of nitrobenzene, and 5 parts by volume of N:N-diethyl-aniline is stirred for 1- hour at 165 C. The solution thus formed is cooled and then diluted with 100parts of ethanol. The isolated dyestuif of the formula is quickly brought to the boil in ethanol of 80% strength. When cool it is separated from the alcohol and dried. The product so obtained contains no chlorine and is light 12 strength fast pure yellow tints when applied according to the dyeing prescription given in Example 1.

Example 14 To a suspension of 18 parts of the aminoanthraquinone of the formula in 100 parts of nitrobenzene are added, at 120 C., 8.8

parts of benzoyl chloride, and the whole is stirred for 30 minutes at 165 C., then diluted with 200 parts of nitrobenzene, and brought quickly to the boil. The solution so obtained is filtered while hot and allowed to 20 cool. The dyestuff of the formula which precipitates in the form of crystals, is isolated by suction filtration, heated quickly to the boil in ethanol, is again isolated by suction filtration, and then dried. The dyestuif so obtained is an intensely yellow product that dyes cotton and regenerated cellulose fast greenish yellow tints when applied according to the dyeing prescription given in Example 1.

The aminoanthraquinone starting material can be prepared as follows:

61.5 parts of a paste of strength of the sodium salt of 1-amino-6-mercapto-anthraquinone are suspended in 1000 parts of water, and heated to C. To the solution so obtained are added, at 60 C., 9.2 parts of allyl 5 chloride, and the whole is stirred for 2 hours at that temll 0 NH perature and then cooled. The precipitated aminoanthraquinone derivative is isolated by suction filtration, washed with water and then dried. When dry, it is in the form brown powder that dyes cotton and regenerated cellulose of a red powder.

NHC O- SOzCH2CH=CH2 ArC OHN in which Ar represents a benzene radical.

3. A vat dyestufi of the formula wherein A represents a l-anthraquinonylamino gro-up bound to :a carbon atom of the ring of the 1,3,5-triazine radical X whose third ring carbon atom bears an allylmercaptophenylamino group.

4. A vat dyestuff consisting of two anthraquinone nuclei linked to one another and bearing in each anthraquinon-e radical an allylmercaptobenzoylamino group.

5. A vat dyestulf consisting of two anthraquinone nuceli linked together and bearing in each anthraquinone radical an allyl-S O r-OC 0 NHEroup 6. Allylmercaptobenzoylaminoaced-ianthrone.

7. Bis-(allylmercaptobenzoylamino)-dianthrirnide carbazole.

8. Bis-(benzoylaminoanthnaquinone)-oxdiazole hearing a CH =CHCH SO substituent in the benzoyl radical.

9. The vat dyestufi' of the formula '14 10. The vat dyestuii of the formula NH-O CSCH2OH=C H2 11. The vat dyestulf of the formula Nllih N S l u 0 O IITH 12. The vat dyestuff of the formula 13. The vat dyestuff of the formula 14. The vat dyestuff of the formula whose third ring-carbon atom bears an a11y1-SO -phenylamino group. wrzOsm-om-or-mom 0 References Cited by the Examiner 5 UNITED STATES PATENTS f 2,657,205 10/1953 Heyna et a1. 260-373 X 0 NH-C C-NH 0 2,658,899 11/1953 Ogilvie 260372 X I f 2,784,204 3/1957 Heyna et a1 260-371 X 10 OTHER REFERENCES Wegmann, Textil Praxis, October 1958, page 1056.

I ll 0 0 WALTER A. MODANC-E, Primaly Examiner.

1 IRVING MARCUS, NICHOLAS S. R=IZZO, Examiners. 15. The vat dyes tuifs of the formula AXA, whereln 15 A represents a l-anthraquinonoylamino group bound to a MARION WESTERN FORD carbon atom of the ring of the 1,3,5-triazine radical X Assistant Examiners. 

1. A VAT DYESTUFF OF THE FORMULA K-(R)N WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE ALLYL-MERCAPTO AND THE ALLYLSULFONE GROUP BOUND TO A CARBON ATOM OF THE VATTABLE CHROMOPHORE K WHICH IS SELECTED FROM THE GROUP CONSISTING OF THE BENZOYLAMINOANTHRAQUINONE, BENZOYLAMINOANTHRIMIDE-CARBAZOLE, BENZOYLAMINOACEDIANTHRONE, ANTHRAQUINOYLAMINO-1:3:5TRIAZINE, ANTHANTHRONE, 2-ANTHRAQUINONYL-ANTHRAQUINONOTHIAZOLE, BIS(AMINOANTHRAQUINONYL)-1:3:4-OXIDAZOLE AND PHTHALOIC ACID - N,N''(DIBENZOYLAMINOANTHRAQUINONYL)AMIDE CHROMOPHORES, AND N REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE WHOLE NUMBERS 1 AND
 2. 